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      Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C( sp 3)−H bonds with alkynes

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          Abstract

          Transition metal-catalyzed enantioselective Sonogashira-type oxidative C( sp 3)—C( sp) coupling of unactivated C( sp 3)−H bonds with terminal alkynes has remained a prominent challenge. The difficulties mainly stem from the regiocontrol in unactivated C( sp 3)—H bond functionalization and the inhibition of readily occurring Glaser homocoupling of terminal alkynes. Here, we report a copper/chiral cinchona alkaloid-based N,N,P-ligand catalyst for asymmetric oxidative cross-coupling of unactivated C( sp 3)—H bonds with terminal alkynes in a highly regio-, chemo-, and enantioselective manner. The use of N-fluoroamide as a mild oxidant is essential to site-selectively generate alkyl radical species while efficiently avoiding Glaser homocoupling. This reaction accommodates a range of (hetero)aryl and alkyl alkynes; (hetero)benzylic and propargylic C( sp 3)−H bonds are all applicable. This process allows expedient access to chiral alkynyl amides/aldehydes. More importantly, it also provides a versatile tool for the construction of chiral C( sp 3)—C( sp), C( sp 3)—C( sp 2), and C( sp 3)—C( sp 3) bonds when allied with follow-up transformations.

          Abstract

          Enantioselective oxidative cross-coupling of unactivated C( sp 3)−H bonds and terminal alkynes is challenging. Here, the authors developed a copper/cinchona alkaloid catalyst for the asymmetric Sonogashira-type alkynylation of C( sp 3)-H bonds via radical intermediates.

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          Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations.

          Chao-Jun Li (2009)
          Synthetic chemists aspire both to develop novel chemical reactions and to improve reaction conditions to maximize resource efficiency, energy efficiency, product selectivity, operational simplicity, and environmental health and safety. Carbon-carbon bond formation is a central part of many chemical syntheses, and innovations in these types of reactions will profoundly improve overall synthetic efficiency. This Account describes our work over the past several years to form carbon-carbon bonds directly from two different C-H bonds under oxidative conditions, cross-dehydrogenative coupling (CDC). We have focused most of our efforts on carbon-carbon bonds formed via the functionalization of sp(3) C-H bonds with other C-H bonds. In the presence of simple and cheap catalysts such as copper and iron salts and oxidants such as hydrogen peroxide, dioxygen, tert-butylhydroperoxide, and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), we can directly functionalize various sp(3) C-H bonds by other C-H bonds without requiring preactivation. We demonstrate (1) reaction of alpha-C-H bonds of nitrogen in amines, (2) reaction of alpha-C-H bonds of oxygen in ethers, (3) reaction of allylic and benzylic C-H bonds, and (4) reaction of alkane C-H bonds. These CDC reactions can tolerate a variety of functional groups, and some can occur under aqueous conditions. Depending on the specific transformation, we propose the in situ generation of different intermediates. These methods provide an alternative to the separate steps of prefunctionalization and defunctionalization that have traditionally been part of synthetic design. As a result, these methods will increase synthetic efficiencies at the most fundamental level. On an intellectual level, the development of C-C bond formations based on the reaction of only C-H bonds (possibly in water) challenges us to rethink some of the most fundamental concepts and theories regarding chemical reactivities. A successful reaction requires the conventionally and theoretically less reactive C-H bonds to react selectively in the presence of a variety of functional groups. With further investigation, we expect that C-C bond formations based on cross-dehydrogenative coupling will have a positive economic and ecological impact on the next generation of chemical syntheses.
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            On the Interpretation of Deuterium Kinetic Isotope Effects in CH Bond Functionalizations by Transition-Metal Complexes

            Eric M Simmons, John Hartwig (2012)
            Article 0 comments Cited 429 times – based on 0 reviews     Review now
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              The Cross-Dehydrogenative Coupling of C sp 3H Bonds: A Versatile Strategy for CC Bond Formations

              Simon Girard, Chao-Jun Li, Thomas Knauber (2014)
              Article 0 comments Cited 314 times – based on 0 reviews     Review now
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                Author and article information

                Contributors
                Xin-Yuan Liu:
                ORCID: http://orcid.org/0000-0002-6978-6465
                liuxy3@sustech.edu.cn
                Journal
                Journal ID (nlm-ta): Nat Commun
                Journal ID (iso-abbrev): Nat Commun
                Title: Nature Communications
                Publisher: Nature Publishing Group UK (London )
                ISSN (Electronic): 2041-1723
                Publication date (Electronic): 12 December 2019
                Publication date PMC-release: 12 December 2019
                Publication date Collection: 2019
                Volume: 10
                Electronic Location Identifier: 5689
                Affiliations
                [1 ]ISNI 0000 0004 1763 3680, GRID grid.410747.1, Shandong Provincial Key Laboratory of Detection Technology for Tumor Markers, School of Chemistry and Chemical Engineering, , Linyi University, ; Linyi, 276005 China
                [2 ]GRID grid.263817.9, Shenzhen Grubbs Institute and Department of Chemistry, , Southern University of Science and Technology, ; Shenzhen, 518055 China
                [3 ]GRID grid.263817.9, Academy for Advanced Interdisciplinary Studies and Department of Chemistry, , Southern University of Science and Technology, ; Shenzhen, 518055 China
                Author information
                http://orcid.org/0000-0002-3840-425X
                http://orcid.org/0000-0002-6978-6465
                Article
                Publisher ID: 13705
                DOI: 10.1038/s41467-019-13705-1
                PMC ID: 6908613
                PubMed ID: 31831750
                SO-VID: e8b36972-e2ae-422d-b6b9-ee617de9b9fe
                Copyright © © The Author(s) 2019
                License:

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                Date received : 1 October 2019
                Date accepted : 20 November 2019
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100007129, Natural Science Foundation of Shandong Province (Shandong Provincial Natural Science Foundation);
                Award ID: ZR2017BB065
                Award Recipient :
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 21804066
                Award ID: 21801116
                Award ID: 21831002
                Award ID: 21722203
                Award Recipient :
                Funded by: Shenzhen special funds for the development of biomedicine, Internet, new energy, and new material industries (No. JCYJ 20180302174416591);Shenzhen Nobel Prize Scientists Laboratory Project (No. C17783101).
                Categories
                Subject: Article
                Custom metadata
                issue-copyright-statement © The Author(s) 2019

                ScienceOpen disciplines: Uncategorized
                Keywords: asymmetric catalysis,asymmetric synthesis,synthetic chemistry methodology
                Data availability:
                ScienceOpen disciplines: Uncategorized
                Keywords: asymmetric catalysis, asymmetric synthesis, synthetic chemistry methodology

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